CN111635736A - Porous alumina-based composite wave-absorbing material and preparation method thereof - Google Patents
Porous alumina-based composite wave-absorbing material and preparation method thereof Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000011358 absorbing material Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 47
- 150000003624 transition metals Chemical class 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 20
- -1 transition metal salt Chemical class 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 18
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 18
- 239000012159 carrier gas Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims description 2
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910052593 corundum Inorganic materials 0.000 description 16
- 239000010431 corundum Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a porous alumina-based composite wave-absorbing material and a preparation method thereof. The preparation method comprises the following steps: pretreating a porous alumina matrix; adding transition metal salt, ammonium fluoride and urea into deionized water, and magnetically stirring until the transition metal salt, the ammonium fluoride and the urea are uniformly mixed to obtain a precursor solution. Immersing the porous alumina matrix in the precursor solution, maintaining the pressure in vacuum, heating for loading, and carrying out phosphating treatment on the loaded product. The porous alumina ceramic not only can meet the requirement of light weight of the wave-absorbing material, but also can adjust electromagnetic parameters and improve impedance matching after being compounded with transition metal phosphide; the electromagnetic wave can generate multiple reflection and scattering when the electromagnetic wave is incident, and the propagation path of the electromagnetic wave in the wave-absorbing material is increased, so that the function of enhancing the wave-absorbing performance is achieved.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a porous alumina-based composite wave-absorbing material and a preparation method thereof.
Background
With the wide application of electronic communication technology and radar positioning technology in the military field, the development of electromagnetic wave absorbing materials with excellent wave absorbing performance and mechanical properties becomes the key point of research of scientists in various countries. The electromagnetic wave absorbing material converts electromagnetic wave energy into heat energy mainly through dielectric loss, magnetic loss and electric conduction loss, thereby achieving the purpose of attenuating the electromagnetic wave. The excellent wave-absorbing material can not only avoid the interference of electromagnetic waves on the operation of mechanical equipment, but also improve the survival capacity of a combat target on a battlefield.
The wave-absorbing materials can be divided into two categories, namely coating type wave-absorbing materials and structural type wave-absorbing materials according to the forming process and the bearing capacity of the wave-absorbing materials. The coating type wave-absorbing material is mainly characterized by small change to equipment, simple and convenient construction and small influence on the maneuvering fire performance of a weapon system. However, the coating type wave-absorbing material is generally composed of a wave-absorbing agent and a binder, and thus has the disadvantages of narrow frequency band, easy falling, poor adhesion and high density. The structural wave-absorbing material has the double functions of bearing and reducing radar scattering cross section (RSC), and has the advantages of light weight and high strength of the composite material. However, the existing structural wave-absorbing material is mostly prepared into the porous structural composite wave-absorbing material by combining a foaming method and a freeze-drying method. The foaming process has high requirements on raw materials, the process conditions are not easy to control, the consistent foaming degree is difficult to ensure during mass production, and the repeatability is poor. Although the freeze-drying method can prepare porous materials with complex structures, the high production cost limits the wide popularization of the freeze-drying method.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a porous alumina-based composite wave-absorbing material and a preparation method thereof. According to the invention, through the combination of the porous alumina and the transition metal phosphide, the electromagnetic parameters of the composite material are optimized, and better impedance matching and attenuation coefficient are obtained, so that excellent wave-absorbing performance is obtained. And the preparation process has low cost and is easy for industrial production.
The invention is realized by adopting the following technical scheme:
the porous alumina-based composite wave-absorbing material comprises a porous alumina matrix and transition metal phosphide growing on the porous alumina matrix.
Further, the porous alumina matrix has an average pore diameter of 30 to 100 μm.
Further, the porosity of the porous alumina matrix is 30% to 70%.
Further, the transition metal phosphide is one or more of iron phosphide, cobalt phosphide, nickel phosphide and copper phosphide.
(II) a preparation method of the porous alumina-based composite wave-absorbing material, which comprises the following steps:
step 1, pretreating a porous alumina matrix to obtain a pretreated porous alumina matrix;
and 2, adding transition metal salt, ammonium fluoride and urea into deionized water, and magnetically stirring until the transition metal salt, the ammonium fluoride and the urea are uniformly mixed to obtain a precursor solution.
Step 3, immersing the pretreated porous alumina matrix in the precursor solution, maintaining the pressure for 20-30min in vacuum, and heating for loading to obtain the porous alumina loaded with the transition metal;
and 4, carrying out phosphating treatment on the porous alumina loaded with the transition metal to obtain the porous alumina-based composite wave-absorbing material.
Further, in step 1, the porous alumina substrate is pretreated, which specifically comprises: sequentially ultrasonically cleaning a porous alumina matrix for 10-15 min by using acetone, absolute ethyl alcohol and deionized water; and then drying the mixture in an oven at the temperature of 60-80 ℃ for 6-10 h.
Further, in the step 2, the concentration of the transition metal ions in the precursor solution is 0.03-0.1 mol/L.
Furthermore, the molar ratio of the transition metal salt, the ammonium fluoride and the urea is 1 (1-2) to (4-5).
Further, in the step 3, the temperature for heating the load is 120-180 ℃, and the heat preservation time is 4-6 hours.
Further, in step 4, the porous alumina loaded with the transition metal is subjected to phosphating treatment, which specifically comprises the following steps:
firstly, respectively placing sodium hypophosphite and transition metal-loaded porous alumina in two crucibles;
secondly, placing the crucible filled with the sodium hypophosphite close to an air inlet of the tubular furnace, and placing the crucible filled with the porous alumina loaded with the transition metal at the middle position of the tubular furnace;
and finally, continuously introducing carrier gas into the tubular furnace, heating to 300-500 ℃ under normal pressure, preserving heat for 2-5 h, and cooling along with the furnace to obtain the porous alumina-based composite wave-absorbing material.
Furthermore, the molar ratio of the sodium hypophosphite to the transition metal element is (1-9): 1.
Further, the carrier gas is an inert gas or a mixed gas of an inert gas and hydrogen.
Compared with the prior art, the invention has the following beneficial effects:
(1) the porous alumina is adopted as a matrix, and the transition metal phosphide is loaded on the matrix to form the porous structure type wave-absorbing material, so that the porous structure type wave-absorbing material has the characteristics of light weight and high strength; the combination of the aluminum oxide and the transition metal phosphide optimizes the electromagnetic parameters of the composite material and obtains better impedance matching and attenuation coefficient, thereby obtaining excellent wave-absorbing performance.
(2) According to the invention, porous alumina is used for providing a porous structure, transition metal phosphide is introduced by a hydrothermal reaction method and a chemical vapor deposition method, the interface bonding force is strong, the impedance matching property is good, the preparation process is simple, the repeatability is good, and a new thought is provided for the large-scale production of the three-dimensional structure composite wave-absorbing material.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention.
Fig. 2 is a reflection loss result diagram of the porous alumina-based composite wave-absorbing material prepared in embodiment 1 of the invention.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
Referring to fig. 1, a preparation method of a porous alumina-based composite wave-absorbing material selects porous alumina with purity of more than 99 wt.%, porosity of 36% and average pore diameter of 70 μm as a matrix. The method specifically comprises the following steps:
step 1, pretreatment: and (3) ultrasonically cleaning the porous alumina matrix for 15min by using acetone, absolute ethyl alcohol and deionized water in sequence. And after the cleaning, drying the porous alumina substrate in an oven at 80 ℃ for 6h to obtain the pretreated porous alumina substrate.
Step 2, preparing a precursor solution: 0.476g of cobalt chloride hexahydrate, 0.148g of ammonium fluoride and 0.6g of urea are weighed and added into 40mL of deionized water, and the mixture is magnetically stirred for 25min until the solution is uniformly mixed to obtain a precursor solution.
Step 3, loading: and (3) putting the pretreated porous alumina matrix and the precursor solution into a 50mL polytetrafluoroethylene inner container, putting the polytetrafluoroethylene inner container into a vacuum drying box, vacuumizing and maintaining the pressure for 30 min. Then the polytetrafluoroethylene liner is placed in a reaction kettle to be screwed and sealed. And then putting the reaction kettle into a 120 ℃ drying oven for heat preservation for 5 hours, taking out the load product in the reaction kettle after the reaction kettle is cooled to room temperature along with the oven, then washing the load product with deionized water, and putting the load product in the 60 ℃ drying oven for drying for 3 hours to obtain the porous alumina loaded with the transition metal.
And 4, phosphorization: 0.8g of sodium hypophosphite is weighed and placed in a corundum crucible, and the porous alumina loaded with transition metal is placed in another corundum crucible. Placing the corundum crucible containing sodium hypophosphite close to the air inlet of the tubular furnace, placing the corundum crucible containing porous alumina loaded with transition metal in the middle position of the tubular furnace, and enabling phosphine gas decomposed by the sodium hypophosphite to flow into another crucible along with carrier gas to react with the porous alumina loaded with the transition metal; and in the reaction process, argon is used as carrier gas, the tubular furnace is heated to 350 ℃ and kept for 2 hours, and the tubular furnace is naturally cooled to room temperature, so that the porous alumina-based composite wave-absorbing material is obtained.
Example 2
Referring to fig. 1, a preparation method of a porous alumina-based composite wave-absorbing material selects porous alumina with purity of more than 99 wt.%, porosity of 40% and average pore diameter of 50 μm as a matrix. The method comprises the following steps:
step 1, pretreatment: and (3) ultrasonically cleaning the porous alumina matrix for 15min by using acetone, absolute ethyl alcohol and deionized water in sequence. And after the cleaning, drying the porous alumina substrate in an oven at 80 ℃ for 6h to obtain the pretreated porous alumina substrate.
Step 2, preparing a precursor solution: 0.808g of ferric nitrate nonahydrate, 0.074g of ammonium fluoride and 0.48g of urea are weighed and added into 40mL of deionized water, and the mixture is magnetically stirred for 30min until the solution is uniformly mixed, so that a precursor solution is obtained.
Step 3, loading: and (3) putting the pretreated porous alumina matrix and the precursor solution into a 50mL polytetrafluoroethylene inner container, putting the polytetrafluoroethylene inner container into a vacuum drying box, vacuumizing and maintaining the pressure for 30 min. Then the polytetrafluoroethylene inner container is placed in a reaction kettle to be screwed and sealed. And then putting the reaction kettle into a drying oven at the temperature of 150 ℃, preserving heat for 5 hours, taking out the load product in the reaction kettle when the reaction kettle is cooled to normal temperature along with the furnace, then cleaning the load product by using deionized water, and placing the load product in the drying oven at the temperature of 60 ℃ for drying for 3 hours to obtain the porous alumina loaded with the transition metal.
And 4, phosphorization: 0.5g of sodium hypophosphite is weighed and placed in a corundum crucible, and the porous alumina loaded with transition metal is placed in another corundum crucible. Placing the corundum crucible containing sodium hypophosphite close to the air inlet of the tubular furnace, placing the corundum crucible containing porous alumina loaded with transition metal in the middle position of the tubular furnace, and enabling phosphine gas decomposed by the sodium hypophosphite to flow into another crucible along with carrier gas to react with the porous alumina loaded with the transition metal; and in the reaction process, using nitrogen as a carrier gas, heating the tubular furnace to 350 ℃, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain the porous alumina-based composite wave-absorbing material.
Example 3
Referring to fig. 1, a preparation method of a porous alumina-based composite wave-absorbing material selects porous alumina with purity of more than 99 wt.%, porosity of 40% and average pore diameter of 100 μm as a matrix. The method specifically comprises the following steps:
step 1, pretreatment: firstly, the porous alumina is sequentially cleaned by acetone, absolute ethyl alcohol and deionized water for 15min by ultrasonic waves. And after the cleaning, drying the porous alumina substrate in an oven at 80 ℃ for 6h to obtain the pretreated porous alumina substrate.
Step 2, precursor solution: then 1.6832g of nickel sulfate hexahydrate, 0.3552g of ammonium fluoride and 1.728g of urea are weighed and added into 80mL of deionized water, and the mixture is magnetically stirred for 30min until the solution is uniformly mixed, so that a precursor solution is obtained.
Step 3, loading: and (3) putting the pretreated porous alumina matrix and the precursor solution into a 100mL polytetrafluoroethylene inner container, putting the polytetrafluoroethylene inner container into a vacuum drying oven, vacuumizing and maintaining the pressure for 20 min. Then the polytetrafluoroethylene inner container is placed in a reaction kettle to be screwed and sealed. And then putting the reaction kettle into a drying oven at the temperature of 150 ℃ and preserving heat for 5 hours, taking out the load product in the reaction kettle when the reaction kettle is cooled to normal temperature along with the furnace, then cleaning the load product by using deionized water, and putting the load product into the drying oven at the temperature of 60 ℃ for drying for 3 hours to obtain the porous alumina loaded with the transition metal.
And 4, phosphorization: 1g of sodium hypophosphite is weighed and placed in a corundum crucible, and porous alumina loaded with transition metal is placed in another corundum crucible. Placing the corundum crucible containing sodium hypophosphite close to the air inlet of the tubular furnace, placing the corundum crucible containing porous alumina loaded with transition metal in the middle position of the tubular furnace, and enabling phosphine gas decomposed by the sodium hypophosphite to flow into another crucible along with carrier gas to react with the porous alumina loaded with the transition metal; and in the reaction process, the mixed gas of 95% argon and 5% hydrogen is used as carrier gas, the tubular furnace is heated to 350 ℃ and kept for 5 hours, and the tubular furnace is naturally cooled to room temperature, so that the porous alumina-based composite wave-absorbing material is obtained.
Example 4
Referring to fig. 1, a preparation method of a porous alumina-based composite wave-absorbing material selects porous alumina with purity of more than 99 wt.%, porosity of 50% and average pore diameter of 65 μm as a matrix. The method specifically comprises the following steps:
step 1, pretreatment: firstly, the porous alumina is sequentially cleaned by acetone, absolute ethyl alcohol and deionized water for 15min by ultrasonic waves. And after the cleaning, drying the porous alumina substrate in an oven at 80 ℃ for 6h to obtain the pretreated porous alumina substrate.
Step 2, preparing a precursor solution: then 0.952g of cobalt chloride hexahydrate, 0.571g of nickel chloride hexahydrate, 0.4263g of ammonium fluoride and 1.92g of urea are weighed and added into 80mL of deionized water, and the mixture is magnetically stirred for 30min until the solution is uniformly mixed, so that a precursor solution is obtained.
Step 3, loading: and (3) putting the pretreated porous alumina matrix and the precursor solution into a 100mL polytetrafluoroethylene inner container, putting the polytetrafluoroethylene inner container into a vacuum drying oven, vacuumizing and maintaining the pressure for 20 min. Then the polytetrafluoroethylene inner container is placed in a reaction kettle to be screwed and sealed. And then putting the reaction kettle into a 180 ℃ oven, preserving heat for 5 hours, taking out the load product in the reaction kettle when the reaction kettle is cooled to normal temperature along with the furnace, then cleaning the load product with deionized water, and putting the load product into a 60 ℃ oven for drying for 3 hours to obtain the porous alumina loaded with the transition metal.
And 4, phosphorization: 1.5g of sodium hypophosphite is weighed and placed in a corundum crucible, and the porous alumina loaded with transition metal is placed in another corundum crucible. Placing the corundum crucible containing sodium hypophosphite close to the air inlet of the tubular furnace, placing the corundum crucible containing porous alumina loaded with transition metal in the middle position of the tubular furnace, and enabling phosphine gas decomposed by the sodium hypophosphite to flow into another crucible along with carrier gas to react with the porous alumina loaded with the transition metal; in the reaction process, the mixed gas of 95% argon and 5% hydrogen is used as carrier gas, the tubular furnace is heated to 400 ℃ and kept for 4 hours, and the mixture is naturally cooled to room temperature, so that the porous alumina-based composite wave-absorbing material is obtained.
In the above examples, the tubular furnace was in a normal pressure state during the phosphating process.
Measuring electromagnetic parameters of the products obtained in the embodiments within the frequency range of 8.2-12.4 GHz by using a vector network analyzer, and calculating corresponding minimum reflection loss values, wherein the results are shown in table 1; meanwhile, the reflectivity curve of the product obtained in example 1 was plotted according to the electromagnetic parameters thereof, as shown in fig. 1.
As can be seen from FIG. 1, the product obtained in example 1 of the present invention has a reflection loss of-19.17 dB at 10.1GHz, a reflection loss value of < -10dB at 8.75-12.11GHz, and an effective bandwidth of 3.36 GHz.
Table 1 wave-absorbing performance test results of the porous alumina-based composite wave-absorbing material obtained in each example
As can be seen from Table 1, the minimum reflection loss value of the product obtained by the invention is-19 to-38 dB, and the effective frequency bandwidth less than-10 dB is 2.18 to 4.08 GHz. The invention can widen the effective frequency bandwidth of the structural wave-absorbing material and improve the wave-absorbing performance of the product.
The porous alumina ceramic matrix has the physical properties of high temperature resistance, good corrosion resistance and large elastic modulus of alumina ceramic, and also has the excellent characteristics of large specific surface area, low thermal conductivity and the like of porous materials, and is widely applied to a plurality of fields of energy conservation, environmental protection, biology, chemical industry and the like in recent years, and the production process is very mature. The porous alumina ceramic is a low-density material with high-temperature strength and toughness, can meet the requirement of light weight of the wave-absorbing material, and can adjust electromagnetic parameters and improve impedance matching after being compounded with transition metal phosphide; the electromagnetic wave can generate multiple reflection and scattering when the electromagnetic wave is incident, and the propagation path of the electromagnetic wave in the wave-absorbing material is increased, so that the function of enhancing the wave-absorbing performance is achieved. In addition, when the porous alumina ceramic is compounded with the transition metal phosphide, more interfaces can be generated, so that the interface loss is enhanced, and the effect of improving the wave absorption performance is achieved.
Although the present invention has been described in detail in this specification with reference to specific embodiments and illustrative embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The porous alumina-based composite wave-absorbing material is characterized by comprising a porous alumina matrix and transition metal phosphide growing on the porous alumina matrix.
2. The porous alumina-based composite wave-absorbing material as claimed in claim 1, wherein the average pore diameter of the porous alumina matrix is 30-100 μm.
3. The porous alumina-based composite wave-absorbing material as claimed in claim 2, wherein the porosity of the porous alumina matrix is 30-70%.
4. The porous alumina-based composite wave-absorbing material of claim 1, wherein the transition metal phosphide is one or more of iron phosphide, cobalt phosphide, nickel phosphide and copper phosphide.
5. A preparation method of a porous alumina-based composite wave-absorbing material is characterized by comprising the following steps:
step 1, pretreating a porous alumina matrix to obtain a pretreated porous alumina matrix;
step 2, adding transition metal salt, ammonium fluoride and urea into deionized water, and magnetically stirring until the transition metal salt, the ammonium fluoride and the urea are uniformly mixed to obtain a precursor solution;
step 3, immersing the pretreated porous alumina matrix in the precursor solution, maintaining the pressure for 20-30min in vacuum, and heating for loading to obtain the porous alumina loaded with the transition metal;
and 4, carrying out phosphating treatment on the porous alumina loaded with the transition metal to obtain the porous alumina-based composite wave-absorbing material.
6. The preparation method of the porous alumina-based composite wave-absorbing material according to claim 5, wherein in the step 2, the concentration of the transition metal ions in the precursor solution is 0.03-0.1 mol/L.
7. The preparation method of the porous alumina-based composite wave-absorbing material as claimed in claim 6, wherein the molar ratio of the transition metal salt to the ammonium fluoride to the urea is 1: 1-2: 4-5.
8. The preparation method of the porous alumina-based composite wave-absorbing material according to claim 5, wherein in the step 3, the temperature of load heating is 120-180 ℃, and the heat preservation time is 4-6 hours.
9. The preparation method of the porous alumina-based composite wave-absorbing material according to claim 5, wherein in the step 4, the porous alumina loaded with the transition metal is subjected to phosphating treatment, and the specific steps are as follows:
firstly, respectively placing sodium hypophosphite and transition metal-loaded porous alumina in two crucibles;
secondly, placing the crucible filled with the sodium hypophosphite close to an air inlet of the tubular furnace, and placing the crucible filled with the porous alumina loaded with the transition metal at the middle position of the tubular furnace;
finally, continuously introducing carrier gas into the tubular furnace, heating to 300-500 ℃ under normal pressure, preserving heat for 2-5 h, and cooling along with the furnace to obtain the porous alumina-based composite wave-absorbing material;
wherein, the carrier gas is inert gas or the mixed gas of the inert gas and hydrogen.
10. The preparation method of the porous alumina-based composite wave-absorbing material as claimed in claim 9, wherein the molar ratio of the sodium hypophosphite to the transition metal element is (1-9) to 1.
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Denomination of invention: A porous alumina based composite absorbing material and its preparation method Granted publication date: 20230808 Pledgee: China Postal Savings Bank Limited by Share Ltd. Huaihua branch Pledgor: HUAIHUA HENG'AN PETROCHEMICAL Co.,Ltd. Registration number: Y2024980007044 |